106565-72-4

Upstream product

• 41609-04-5 N-benzyl-3-amino-2-cyclohexen-1-one 
• 61475-92-1 (2R,4aS,5S,8aR)-1-Benzyl-5-methyl-2-propyl-decahydro-quinoline 
• 5978-08-5 1-chloro-4-(1,3-dioxolane)-n-pentane 
• 86963-75-9 1-Benzyl-5-methyl-2-propyl-1,2,3,4,5,6,7,8-octahydro-quinoline-5-carbonitrile 
• 61475-92-1 (rac)-(2R,4aS,5R,8aS)-1-benzyl-5-methyl-2-propyl-decahydroquinoline 
• 3695-28-1 5-iodo-2-pentanone ethylene ketal 
• 106488-75-9 (S)-8-Methyl-3-phenyl-5-propyl-decahydro-oxazolo[2,3-j]quinoline 
• 86963-75-9 (2R,5R)-1-Benzyl-5-methyl-2-propyl-1,2,3,4,5,6,7,8-octahydro-quinoline-5-carbonitrile 
• 86963-81-7 (2S,6S)-1-Benzyl-2-(4-oxo-pentyl)-6-propyl-piperidine-2-carbonitrile 
• 844638-85-3 4-azido-hept-1-ene 
• 166903-57-7 methanesulfonic acid 1-propyl-but-3-enyl ester 
• 5622-72-0 1-Propyl-but-3-enylamine 
• 3521-91-3 hept-1-en-4-ol 
• 154309-15-6 1-Benzyl-5-hydroxy-octahydro-quinolin-2-one 

Downstream Products

• 55785-30-3 (2R^*,4aS^*,5S^*,8aR^*)-2-(1-propyl)-5-methyldecahydroquinoline hydrochloride 

Relevant academic research and scientific papers

Studies on difficult intramolecular hydroaminations in the context of four syntheses of alkaloid natural products

Examples of intramolecular alkene hydroaminations forming six-membered ring systems are rare, especially for systems in which the double bond is disubstituted. Such cyclizations have important synthetic relevance. Herein we report a systematic study of these cyclizations using recently developed Cope-type hydroamination methodologies. Difficult intramolecular alkene hydroaminations were used as key steps in syntheses of 2-epi-pumiliotoxin C, coniine, N-norreticuline and desbromoarborescidine A. This effort required the development of optimized hydroamination conditions to improve the efficiency of the cyclizations. Collectively, our results show that Cope-type cyclizations can be achieved on a variety of challenging substrates and proceed under similar conditions for both N-H and N-substituted hydroxylamines.

Oxazolone cycloadducts as heterocyclic scaffolds for alkaloid construction: Synthesis of (±)-2-epi-pumiliotoxin C

Intramolecular Diels-Alder cycloaddition of N-substituted oxazolone triene I allows direct entry to the functionalized octahydroquinoline II. Further manipulation of this framework by stereo- and regioselective introduction of the 5-methyl substituent, fo

Diastereoselective synthesis of 2,5-disubstituted decahydroquinolines via ring-rearrangement metathesis and zirconium-mediated cyclization

A diastereoselective approach to 2,5-substituted decahydroquinolines by zirconium-mediated cyclization of unsaturated α,α′- disubstituted piperidines II is described. The required piperidines could be obtained from secondary sulfonamides III via ruthenium-catalyzed ring-rearrangement metathesis (RRM) in high yields. Racemic trans-195A and 2-epi-trans-195A were synthesized in 8 steps starting with butyraldehyde and cyclohex-2-enol.

Use of an acetylenic sulfone as an alkene dipole equivalent in the synthesis of (±)-pumiliotoxin C

The cycloaddition of methyl cis-2-amino-trans-6-methylcyclohexanecarboxylate (3) with 1-p-(toluenesulfonyl)-1-pentyne (4) afforded the corresponding enaminone 2, that was in turn reduced to (±)-pumiliotoxin C (1). The acetylenic sulfone 4 thus functions as the synthetic equivalent of the alkene dipole 5 in this process.

'Decahydroquinoline construction through aza-annulation: A stereoselective synthesis of (±)-5-epipumiliotoxin C.'

Aza-annulation of activated acrylic acid derivatives with 3-benzylamino-2-cyclohexenone led to the efficient formation of the corresponding bicyclic lactam. Stereospecific hydrogenation of this unsaturated lactam resulted in the selective formation of the cis fused bicyclic alkaloid, and subsequent elaboration at C-5 and C-2 completed the synthesis of the decahydroquinoline alkaloid (±)-5-epipumiliotoxin C.

α-alkylation and stereochemistry of cis- and trans-decahydroquinolines mediated by the formamidine and boc activating groups. Synthesis of pumiliotoxin C 1

cis- and trans-decahydroquinolines, as their t-Boc and formamidine derivatives, have been metalated and alkylated. The former gives mainly axial alkylation whereas the latter gives equatorial alkylation in the trans series. For the cis series, the t-Boc derivative gives essentially pure equatorial alkylation as does the formamidine derivative. Several electron-transfer processes occur simultaneously with the ionic alkylation, and this can be altered by use of pentynylcopper or HMPA. Furthermore, cuprates, when employed, gave good yields of alkylation product via radical pathways, but the stereochemistry suffered. A synthesis of the poison dart frog secretion, pumiliotoxin C, has been accomplished using these alkylation techniques.

Stereospecific Total Syntheses of Decahydroquinoline Alkaloids (+/-)-195A and (+/-)-2-epi-195A

The total syntheses of decahydroquinoline alkaloids (+/-)-195A (pumiliotoxin C) and (+/-)-2-epi-195A are described.An unexpected, stereospecific epimerization of the C2 stereocenter of intermediate 6a occurred during its reduction.The isomerization result

Octahydroquinoline Syntesis via Immonium Ion Based Diels-Alder Chemistry: Synthesis of (-)-8a-Epipumiliotoxin C

A total synthesis of (-)-8a-epipumiliotoxin C has been developed which features an intramolecular immonium ion based Diels-Alder reaction.Cyclocondensation of the immonium ion 8 derived from optically pure aldehyde 2 and ammonium chloride provided two octahydroquinolines 9 and 10, in a ratio of 2.2:1.The formation of 9 and 10 is rationalized on the basis of the chair-like conformations 16 and 17 respectively.Reduction of the double bond in 9 affored (-)-8a-epipumiliotoxin C.

Asymmetric synthesis. VIII. Biogenetically patterned approach to the chiral total synthesis of (-)-pumiliotoxin-C

(-)-Pumiliotoxin-C and the (+)-9,10-trans isomer 10 were prepared in six steps from the chiral (+)-2-cyano-6-oxazolopiperidine synthon 3.

2-CYANO Δ PIPERIDINES VIII: BIOMIMETIC APPROACH TO THE SYNTHESIS OF THE DECAHYDROQUINOLINE RING SYSTEM OF POISON-DART FROG TOXINS

A biomimetic approach towards the synthesis of pumiliotoxin C has been developed.The key transformation of enamine equivalent 8 to 9 was catalyzed by contact with alumina.Cyclized intermediate 9 was then reduced stereospecifically to the trans decahydroqu